KR102038180B1 - A novel transition metal based pro-catalyst and a process for its preparation - Google Patents

Abstract

화학식 I
여기서 치환기들은 설명서에서 정의된 의미를 가진다. 본 발명은 또한 화학식 I에 의해 표현되는 전이 금속 기반 전촉매 제조 공정에 관한 것이며 이로 부터 수득된 촉매 조성물에 관한 것이다. 또한, 본 발명은 화학식 I에 의해 표현되는 전이 금속 기반 전촉매를 포함한 촉매 조성물을 이용하여 올레핀을 중합하는 공정에 관한 것이다.The present invention is a transition metal based procatalyst represented by formula (I):

Formula I
Substituents have the meanings defined in the description. The invention also relates to a process for preparing a transition metal based procatalyst represented by formula (I) and to a catalyst composition obtained therefrom. The present invention also relates to a process for polymerizing olefins using a catalyst composition comprising a transition metal based procatalyst represented by formula (I).

Description

A NOVEL TRANSITION METAL BASED PRO-CATALYST AND A PROCESS FOR ITS PREPARATION

The present invention relates to a procatalyst and a manufacturing process thereof. The invention also relates to the use of said procatalyst in the polymerization reaction.

Polymeric polyolefins have physical properties such as high wear resistance, high impact strength and low friction coefficient. Therefore, there is a high demand for various types of polymer polyolefins such as fibers and sheets, biomaterials, wires, and cables. Polyolefins with molecular weights larger than 1 million g / mol, generally referred to as ultrahigh molecular weight polyolefins, have gained popularity as multifunctional applications in many fields, from biomedical to ballistic materials. Ultra-high molecular weight polyethylene with minimal intertwined polymer chains shows porosity, high crystallinity and interesting solid-state applications below the melting point, which makes it possible to use artificial organ techniques, except in defense applications where high impact strength is required. It is suitable for biomedical applications such as polymeric supports in the three-dimensional regeneration and substitution of tissues.

Polyolefins are known to be produced using transition metal-catalyzed polymerization techniques. Typically, the catalysts used to produce polyolefins are largely multi-site heterogeneous Ziegler-Natta catalysts. With advances in polymerization technology, single site catalysts or group (IV) metallocene catalysts are increasingly being used to produce polyolefins. Single site catalysts and metallocene catalysts are constantly being designed to meet important production process requirements. Improvements in the catalyst proceeded to achieve fouling of the zero or near zero used equipment and to maintain catalytic activity. Advances in these catalysts in the synthetic ability to impart various desirable properties to the final product require careful selection of the catalyst composites. In addition, the selection of suitable ligands to be complexed with the metal component of the catalyst is carried out to impart the desired properties to the final product.

For example, ethylene polymerization catalyzed by homogeneous single site catalysts involves electron exchange between the ligand and the metal. Literature has been reported to play a role in determining the activity as well as the stereo-specificity of the catalyst. Inherently, the ligands are electronically flexible and thus impart high activity to the resulting catalyst composite, as well as meeting the need to tailor them to achieve the desired molecular weight and porosity, morphology, bulk density and high crystallinity of the resulting polymer.

Intensive research has led to the discovery of a number of highly active catalysts for the polymerization of ethylene, which include phenoxy-imine ligand early transition metal complexes (FI catalysts), pyrrolid-imine ligand group IV transition metal complexes (PI catalysts), indoleide -Imine ligand Ti complex (II catalyst), phenoxy-imine ligand group (IV) transition metal complex (IF catalyst), phenoxy-ether ligand Ti complex (FE catalyst), imine-pyridine ligand late transition metal complex (IP catalyst) ), Tris (pyrazolyl) borate ligand Ta complex (PB catalyst). Some prior arts are discussed below.

CN101280031 discloses a process for preparing a catalyst system comprising a 5,5-isopropylidene-bis (3-tert-butyl-hydroxybenzaldehyde) imine ligand complexed with a transition metal. This catalyst system reacts 5,5-isopropylidene-bis (3-tert-butyl-hydroxybenzaldehyde) with a mono-amine to yield a ligand, which subsequently complexes with a transition metal compound.

CN101089006 discloses a nickel-based salicy aldehyde bridged binuclear carbodiimide type compound. The nickel-based catalyst disclosed in CN101089006 produces polymers having a molecular weight in the range limited to only 1 lakh when used in polymerization reactions.

[O, N] -type ligands were described in an article entitled "Arene-bridged salicylidimine-based binuclear neutral nickel complexes: synthesis and ethylene polymerization activity" published in Organometallic 2007, 26, 617-625. Disclosed is a nickel based catalyst having.

Another article entitled "Ethylene and Propylene Polymerization of Bis (Phenoxy-Imine) Titanium Complexes," published by Rieko Furuyama et al., Published in Journal of Molecular Catalysis, Chapter A: Chemicals 200 (2003) 31-42. The article discloses titanium-based catalysts for ethylene and propylene polymerization. A ligand obtained by reacting 3-t-butyl salicyaldehyde / 3, 5-di-t-butyl salicyaldehyde with mono-amine is complexed with titanium halide to prepare a catalyst.

"Transition metal complexes of tetradentate and didentate ligand bases as catalysts for ethylene polymerization, published by MarzenaBialek et al, in Magazine Polymer Science: Chapter A: Polymer Chemistry, Vol. 47, 565-575 (2009): Another article entitled "The Action of Transition Metals and Cocatalysts" discloses catalysts based on transition metals such as vanadium and titanium, zirconium. The ligand complex of this catalyst is prepared by reacting ortho-phenylenediamine with salicyaldehyde, which is subsequently complexed with a transition metal to obtain a catalyst.

WO2013118140 discloses a chemically immobilized heterogeneous polymerization catalyst having salicyaldehyde imine ligand complexed with a transition metal compound supported by a functionalized organic support.

An article by Prof. Ibrahim M. AlNajjar and entitled “New Catalysts for Olefin Polymerization,” published in the Saudi International Petrochemical Conference, 2011, describes a transition metal-based catalyst employing para-phenylenediamine for preparing ligand complexes. To start.

A FI catalyst has also been disclosed in an article entitled "FI Catalysts for Principles and Practices of Olefin Oligomerization and Polymerization" by Terunori Fujita .

Some prior art catalysts are less effective at polymerizing olefins to achieve polymers having molecular weights in the range of 1 million g / mol. Also, catalysts known in the prior art under ambient temperature and high pressure exhibited a fast kinetics profile, which, combined with the active nature of some catalysts, presents challenges to controlling the molecular weight of the polymer. The problem of controlling the molecular weight is also exacerbated in obtaining low molecular weight polymers ranging from 1 million g / mol to 6 million g / mol due to uncontrollable rates. This generally increases the reaction temperature well above 65 ^° C., and if this temperature is not effectively relaxed, it will result in the formation of polymer masses in the reactants. This in turn ends with fouling in the polymerization unit. Therefore, in the end, the use of catalysts known in the prior art would require frequent maintenance which would increase the operating costs for the polymerization process.

Accordingly, there is a need to develop catalysts for polymerization reactions having improved reaction rate control, minimum operating costs, and molecular weight control properties.

Some objects of the present invention are discussed as follows.

One object of the present invention is to alleviate one or more problems of the prior art or to provide at least a useful alternative.

It is yet another object of the present invention to provide a transition metal based procatalyst.

It is yet another object of the present invention to provide a transition metal based procatalyst for olefin polymerization producing polyolefins having ultra high molecular weight.

It is yet another object of the present invention to provide a transition metal based procatalyst with improved reaction rate control resulting in a controlled polymer molecular weight.

Another object of the present invention is to provide a transition metal based procatalyst with improved reaction rate control to eliminate fouling of the polymerization unit.

It is yet another object of the present invention to provide a simple and economical transition metal based procatalyst manufacturing process.

Another object of the present invention is to provide an olefin polymerization process using a transition metal based procatalyst.

Another object of the present invention is to provide a procatalyst suitable for both heterogeneous and homopolymerization processes.

Yet another object of the present invention is to provide a catalyst composition comprising a procatalyst.

Other objects and advantages of the invention will be apparent from the following description, which is not intended to limit the scope of the invention.

In one aspect of the invention there is provided a transition metal based procatalyst, which is as Formula I:

b. Formula I

Wherein R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ , R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl, halide;

R ⁵ and R ⁹ are tertiary alkyl groups;

R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;

R ^{3 is} independently selected from hydrogen and halogen, alkoxy, aryloxy, carboxyl group, sulfone group;

M is a group consisting of hafnium (Hf), manganese (Mn), iron (Fe), rhenium (Re), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V), and titanium (Ti) Is a transition metal selected from;

X is a halide selected from the group consisting of Cl, Br, I; n is an integer of 2.

Typically, the procatalyst consists of a set of substituents selected from the group consisting of

i. R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ _, R ¹⁰ , R ¹¹ , R ¹² are hydrogen; R ⁵ and R ⁹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer 2;

ii. R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁸ _, R ¹⁰ , R ¹² are hydrogen; R ⁵ and R ⁹ , R ⁷ and R ¹¹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer of 2.

In another aspect of the invention there is provided a transition metal based procatalyst manufacturing process, the process comprising:

i. Reacting the aromatic diamine of formula (II) with at least one substituted salicyaldehyde of formula (IIIa / IIIb) to obtain a sieve base imine ligand of formula (IV),

Formula (II) Formula (IIIa) Formula (IIIb) Formula (IV)

Wherein R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ , R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl, halide;

R ⁵ and R ⁹ are tertiary alkyl groups;

R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;

R ^{3 is} independently selected from hydrogen and halogen, alkoxy, aryloxy, carboxyl group, sulfone group;

Ii. Adding an alkali metal ion to the ship base imine ligand of formula (IV) using an alkali metal ion additive to obtain an alkali metal salt of the ship base imine ligand of formula (V),

Formula (IV) Formula (V)

R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ , R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl, halide;

R ⁵ and R ⁹ are tertiary alkyl groups;

R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;

R ^{3 is} independently selected from hydrogen and halogen, alkoxy, aryloxy, carboxyl group, sulfone group;

M ₁ is an alkali metal ion of an alkali metal ion additive.

Iii. Chelating either the Schiff base imine ligand of Formula IV or the Schiff base imine ligand of Formula (V) with a transition metal halide to obtain a transition metal based procatalyst represented by Formula I:

               Formula I

Wherein R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ , R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl, halide;

R ⁵ and R ⁹ are tertiary alkyl groups;

R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;

R ^{3 is} independently selected from hydrogen and halogen, alkoxy, aryloxy, carboxyl group, sulfone group;

M is a group consisting of hafnium (Hf), manganese (Mn), iron (Fe), rhenium (Re), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V), and titanium (Ti) Transition metal selected from;

X is a halide selected from the group consisting of Cl, Br, I;

 n is an integer of 2.

Typically, the ratio of alkali metal salt and transition metal halide of the Schiff base imine ligand or Schiff base of Formula IV is 1: 1.

Typically, step (i) consists of p-toluene sulfonic acid and sulfuric acid dissolved in at least one liquid medium selected from the group consisting of toluene and xylene, hexane, methanol and ethanol at a temperature from 40 ^o C to the boiling point of the liquid medium. Run in the presence of at least one selected from the group.

Typically, the substituted salicyaldehyde is at least one compound selected from the group consisting of 3-tert-butyl salicylaldehyde and 3,5-di-tert-butyl salicylaldehyde.

Typically, substituted salicylates of formula (IIIa) and substituted salicylates of formula (IIIb) are the same or different.

Typically, the procatalyst is a set of substituents selected from the group consisting of:

R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ _, R ¹⁰ , R ¹¹ , R ¹² are hydrogen; R ⁵ and R ⁹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is integer 2

R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ _, R ¹⁰ , R ¹¹ , R ¹² are hydrogen; R ⁵ and R ⁹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer 2;

R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁸ _, R ¹⁰ , R ¹² are hydrogen; R ⁵ and R ⁹ , R ⁷ and R ¹¹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer 2.

Typically, the alkali metal ion additive is one selected from the group consisting of n-butyl lithium and sodium hydride, lithium aminoalkoxide, lithium diisopropylamide.

In one aspect of the invention there is provided a catalyst composition comprising:

a. Transition metal based procatalysts of Formula (I);

         Formula I

Wherein R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ , R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl, halide;

R ⁵ and R ⁹ are tertiary alkyl groups;

R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;

R ^{3 is} independently selected from hydrogen and halogen, alkoxy, aryloxy, carboxyl group, sulfone group;

M is a group consisting of hafnium (Hf), manganese (Mn), iron (Fe), rhenium (Re), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V), and titanium (Ti) Transition metal selected from;

X is a halide selected from the group consisting of Cl, Br, I;

 n is an integer of 2.

b. At least one alkyl aluminum co-catalyst

c. At least one inert hydrocarbon liquid medium

Typically, alkyl aluminum co-catalysts are methylaluminoxane and poly-methylaluminosane, triethyl aluminum, isoprenyl aluminum, aluminum sesquichloride, tri-n-octyl aluminum, triiso At least one compound selected from the group consisting of butyl aluminum.

In one embodiment, the cocatalyst is polymethylaluminosane.

Typically, the ratio of elemental aluminum to elemental titanium (Al / Ti) is 50: 1-1000: 1.

Typically, the inert hydrocarbon liquid medium is at least one selected from the group consisting of pentane and hexane, cyclohexane, methyl cyclohexane, heptane, octane, decane, toluene, isopentane, barsol.

In one embodiment of the present invention, the ratio of elemental aluminum to elemental titanium (Al / Ti) is 200: 1 -300: 1 and the inert hydrocarbon liquid medium is barsol.

In another embodiment of the invention, an olefin polymerization process is provided, the process comprising:

i. The transition metal based procatalyst of claim 1 and at least one co-catalyst are mixed at a temperature of 10 ° C.-30 ° C. in a ratio of elemental aluminum to elemental titanium of 50: 1 to 1000: 1 and in the presence of an inert hydrocarbon liquid medium. To obtain an active catalyst composition,

ii. Adding at least one olefin monomer to the active catalyst composition to obtain a reaction mixture,

iii. The reaction mixture was polymerized at a pressure of 0.1-11 bar at a temperature of 5 ° C.-70 ° C. for 1 hour-10 hours to obtain a polymerized olefin.

According to another aspect of the present invention, there is provided a polyolefin obtained by the above-described process, wherein the polyolefin is dis-entangled ultra high molecular weight and has at least one of the following features.

i. Bulk density of 0.05-0.1 g / cc;

ii. Molecular weight of 1 million g / mol-6 million g / mol;

iii. Crystallinity of 90-99%;

iv. Intrinsic viscosity of 10-32 dl / g;

v. Fiber and porous form.

Typically, the inert hydrocarbon liquid medium is at least one selected from the group consisting of pentane and hexane, cyclohexane, methyl cyclohexane, heptane, octane, decane, toluene, isopentane, barsol.

In one embodiment of the invention, the olefin monomer is ethylene and the inert hydrocarbon liquid medium is bar sol.

1 shows a comparative rate profile of a polymerization reaction using a transition metal based procatalyst (A) with a prior art catalyst;
2 shows the action of a co-catalyst / catalyst (Al / Ti) on a transition metal based procatalyst (A) and a polymerization profile using prior art catalysts;
3 shows the mass spectra taken in the EI (electron ionization) mode for the procatalyst (A);
4 shows the mass spectrum taken in CI (chemical ionization) mode for the procatalyst (A);
5 shows the mass spectra taken in the EI (electron ionization) mode for the procatalyst (B);
6 shows the present invention SEM images of one representative polymer obtained using a procatalyst are shown;
7 shows the present invention XRD of one representative polymer obtained using a procatalyst is shown.

According to one aspect of the present invention, a transition metal based procatalyst is provided which can be used in the polymerization of olefins to produce dis-entangled ultra-polymeric polyolefins.

The novel transition metal based procatalyst of the present invention is represented by Formula I:

d. Formula I

Substituents of formula (I) R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ , R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl, halide. R ⁵ and R ⁹ in formula I are tertiary alkyl groups, while R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and tertiary alkyl groups.

R ³ is also selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl group, sulfone group.

M of Formula I is hafnium (Hf) and manganese (Mn), iron (Fe), rhenium (Re), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V), titanium (Ti) Transition metal selected from the group consisting of:

N in formula (I) is the number of X ions satisfying the atomic value of the transition metal ion and is 2.

In one embodiment the substituents of formula (I) are as follows:

R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ _, R ¹⁰ , R ¹¹ , R ¹² are hydrogen; R ⁵ and R ⁹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer 2.

In another embodiment, the substituents of formula (I) are defined as follows:

R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁸ _, R ¹⁰ , R ¹² are hydrogen; R ⁵ and R ⁹ , R ⁷ and R ¹¹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer 2.

In another aspect of the invention there is provided a process for preparing a transition metal based procatalyst of formula (I).

The transition metal based procatalyst manufacturing process of the present invention is described below.

In a first step, the aromatic diamine of formula (II) and at least one salicyaldehyde of formula (IIIa / IIIb) are reacted to obtain a sieve base imine ligand of formula (IV). The reaction is at least one selected from the group consisting of p-toluene sulfonic acid and sulfuric acid dissolved in at least one liquid medium selected from the group consisting of toluene, xylene, hexane, methanol and ethanol at a temperature of 40 ^° C to the boiling point of the liquid medium. Is executed in the presence of.

This reaction is represented schematically as follows.

Formula (II) Formula (IIIa) Formula (IIIb) Formula (IV)

Substituents II, IIIa, IIIb, and IV are defined as follows:

R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ , R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl, halide; R ⁵ and R ⁹ are tertiary alkyl groups; R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group; R ³ is selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl group, sulfone group.

In the last step, the sieve base imine ligand of formula IV obtained in step 1 is chelated with the transition metal halide to obtain the transition metal based procatalyst of the present invention represented by formula I.

In another embodiment, the process for preparing a transition metal based procatalyst of the present invention is such that the seed base imine ligand of formula (IV) is reacted with an alkali metal ion additive to obtain an alkali metal salt of the seed base imine ligand of formula (V). Accompany the steps. The alkali metal salt formation reaction is represented schematically as follows:

    Formula (IV) Formula (V)

Wherein the substituents R ¹ and R ² , R ⁴ , R ⁶ R ⁸ _, R ¹⁰ _, R ¹² R ⁵ , R ⁹ and R ⁷ _, R ¹¹ , R ³ are as defined above and M ₁ is an alkali of an alkali metal additive Metal ions.

The alkali metal salt of the Schiff base imine ligand of Formula V is then chelated with a transition metal halide to obtain the transition metal based procatalyst of the present invention represented by Formula I.

The inventors of the present invention have conducted experiments that the ratio of alkali metal salts to transition metal halides of the Schiff base imine ligand of Formula IV or the Schiff base imine ligand of Formula (V) plays a vital role in determining the type of procatalyst. Found. For example, if the ratio of alkali metal salts to transition metal halides of the Schiff base imine ligand of Formula IV or the Schiff base imine ligand of Formula (V) is 1: 1, then the product obtained is a mono- represented by formula (I). It is a chelated procatalyst.

The term "alkali metal salt formation" or "alkali metal ion addition" or "alkali metal salt of" in the context of the present invention means that the alkali metal ion is attached to the organic molecule at the hydroxyl oxygen position by substituting the hydrogen ions of the hydroxyl group. Means a chemical reaction.

In addition, if the ratio of the seed base imine ligand of the formula IV or formula V to the transition metal halide is 2: 1, the obtained product is a procatalyst comprising a bis-chelated ligand.

In addition, to prepare a procatalyst comprising a tris-chelated ligand, the ratio of the sieve base imine ligand to the transition metal halide of Formula IV or Formula V should be maintained at 3: 1.

Alkali metal ion additives selected for the formation of salts of the sieve base imine ligands of formula (IV) include, but are not limited to, n-butyllithium and sodium hydride, lithium aminoalkoxides, lithium diisopropylamides, and combinations thereof.

In one embodiment, the substituted salicyaldehyde of formula (IIIa) and substituted salicyaldehyde of formula (IIIb) are the same used to obtain the seed base imine ligand of formula (IV).

In another embodiment, the substituted salicyaldehyde of formula (IIIa) is different from the salicylate of formula (IIIb), which is used to obtain the seed base imine ligand of formula (IV).

The transition metal halides used in the process of the present invention are hafnium (Hf) halides and manganese (Mn) halides, iron (Fe) halides, rhenium (Re) halides, tungsten (W) halides, niobium (Nb) halides, tantalum ( Ta) halides, vanadium (V) halides, titanium (Ti) halides, and combinations thereof, halides are selected from the group consisting of chlorides, bromide and iodide. Titanium tetrachloride is preferably used as transition metal halide for the purposes of the present invention.

In one embodiment, the transition metal based procatalyst of the present invention may be used as a homogeneous procatalyst for polymerizing olefins.

The transition metal-based procatalyst of the present invention is converted to a heterogeneous catalyst by applying various known immobilization techniques involving the use of inorganic oxides, organic supports, other inorganic supports, other macromolecules such as dendrimers, and polymer supports. It could be. The transition metal based procatalyst and the support of the present invention are bonded to each other by a bond, including but not limited to covalent bonds and hydrogen bonds, coordination bonds, coordination covalent bonds, and physical bonds.

According to another aspect of the present invention, a catalyst composition is provided. The catalyst composition comprises a transition metal based procatalyst represented by formula I and at least one alkyl aluminum, co-catalyst, at least one inert hydrocarbon liquid medium. The precatalyst and co-catalyst must be put together in an inert hydrocarbon medium to prepare the catalyst composition. However, due to the nature of the organic ligands of the procatalyst, the procatalyst cannot be directly dissolved in the inert hydrocarbon liquid medium. Therefore, the procatalyst is first dissolved in a solvent such as toluene and then comes into contact with a suspension of an inert hydrocarbon liquid medium containing alkyl aluminum.

Co-catalysts useful for the preparation of catalyst compositions include methylaluminosane and poly-methylaluminosane, triethyl aluminum, isoprenyl aluminum, aluminum sesquichloride, tri-n-octyl aluminum, triisobutyl aluminum And alkyl aluminum compounds selected from the group consisting of combinations thereof. Specifically, poly-methylaluminosane is used as co-catalyst.

The ratio of elemental aluminum to elemental titanium (Al / Ti) is important in the polymerization reaction. Thus, the ratio of elemental aluminum to elemental titanium amounts to 50: 1-1000: 1, specifically the ratio is 200: 1 -300: 1.

Examples of inert hydrocarbon liquid media useful for the purposes of the present invention include, but are not limited to, pentane and hexane, cyclohexane, methyl cyclohexane, heptane, octane, decane, toluene, isopentane, barsol. After a series of experiments, the inventors of the present invention found that barsol is the most suitable inert hydrocarbon liquid medium.

According to another aspect of the present invention there is provided a process for polymerizing an olefin using the transition metal based procatalyst of the present invention represented by formula (I) to obtain a dis-entangled ultra-polymer polyolefin.

Using the transition metal-based procatalyst of the present invention, suitable nanos such as carbon nanotubes (single, multi-walled, etc.), silica and graphene, including all nanomaterials, optionally in co- or co-polymerization mode Olefin polymerization can be carried out in the presence of a particle aid.

The polymerization of the olefins can be carried out under ambient temperature conditions and pressures in the presence of a liquid medium above the boiling point and in the presence of aluminum alkyls suitable as procatalysts, activators of the invention.

According to the invention, in the first step, the transition metal based procatalyst is activated by treatment with at least one alkyl aluminum compound under suitable conditions. Alkyl aluminum compounds include methylaluminosane and poly-methylaluminosane, triethyl aluminum, isoprenyl aluminum, aluminum sesquichloride, tri-n-octyl aluminum, triisobutyl aluminum, and combinations thereof But not limited to this. In an exemplary embodiment of the invention, the alkyl aluminum compound is poly-methylaluminosane. The ratio of aluminum to titanium is maintained at 50: 1 to 1000: 1 to fully activate the transition metal based procatalyst. The activity of the procatalyst is achieved by adding the cocatalyst suspended in an inert hydrocarbon liquid medium to the precatalyst dissolved in toluene of the polymerization unit prior to initiation of the polymerization process. Inert hydrocarbons used as liquid medium during activation of the catalyst include, but are not limited to, groups consisting of pentane and hexane, cyclohexane, methyl cyclohexane, heptane, octane, decane, toluene, isopentane, barsol, combinations thereof Do not.

The inert hydrocarbon used as liquid medium during the activation of the catalyst is bar sol.

The method step of catalyst activation is carried out under an inert atmosphere at a temperature of 10 ° C-30 ° C.

In the second step, olefin monomers having 2-18 carbon atoms are added to the active catalyst to obtain a reaction mixture. The reaction mixture is subsequently polymerized at a pressure of 0.1 to 11 bar at a temperature of −5 ° C. to 70 ° C. for 1 to 10 hours to obtain an unwrapped ultra-polymer polyolefin. The molecular weight of the polyolefin obtained is in the range of 1 million g / mol to 6 million g / mol. As known to those skilled in the art of olefin polymerization, the process conditions can be suitably varied during polymerization to further increase the molecular weight of the polymer produced using this catalyst composition. The high entanglement properties of polyolefins prepared using the catalyst compositions of the present invention are related to the structure and properties of the ligands present in the procatalyst. Ligands based on aromatic diamines and substituted salicyaldehydes regulate the electronic and geometric environment around the central titanium of the catalyst to produce unwrapped ultra-polymeric polyolefins. The procatalyst of the present invention also contributes to controlling the rate of polymerization. The co-catalyst also interacts with the procatalyst of the present invention to form cationic complexes, which control the molecular weight of the resulting polyolefin and terminate the polymerization reaction at the necessary stages.

In an exemplary embodiment of the present invention, polymerization of ethylene was carried out using the transition metal based procatalyst of the present invention. The resulting polyethylene is highly disentangled. The degree of annealing was observed by running a test such as sheet formation under pressure under the melting temperature. It has also been observed that the sheets can be pulled out with high strength films, tapes and fibers of over 1 GPa. The polyethylene obtained was molded into different forms of high strength.

Polyethylene obtained using a transition metal based catalyst of formula (I) shows the following properties:

A bulk density of 0.05-0.1 g / cc;

90-99% crystallinity;

A molecular weight of 1 million g / mol 6 million g / mol;

An intrinsic viscosity of 10-32 dl / g;

-Fibrous and porous forms.

The invention is illustrated by the following non-limiting examples.

Examples

Example 1:

Step A: Preparation of Ship Base Imine Ligand (C)

All operations were carried out in nitrogen atmosphere. m-phenylenediamine (1.08 g, 10 mmol), 3-tert butyl salicylicaldehyde (3.42 mL, 20 mmol) and p-toluene sulfonic acid (10 mg) were dissolved in anhydrous toluene (50 mL) and the mixture at 110 ^° C. Stirred under nitrogen atmosphere for 5 hours. The resulting mixture was condensed in vacuo to yield crude sheep base imine ligand (C) as a dark brown solid. The crude seed base imine ligand (C) was purified by column chromatography on silica gel using n-hexane / ethyl acetate (100: 1) as the eluent to give the pure product, the ship base imine ligand (C) as a light orange solid. (3.6 g; yield 85%).

Ship Base Imine Ligand

         (C)

Step B: Lithiation of the Ship Base Imine Ligand followed by Chelation with Titanium Tetrachloride

Seep base imine ligand (C) 1: 1 (ligand: TiCl ₄ ) or mono chelate (A)

All operations were performed under nitrogen atmosphere. Seef base imine ligand (C) (1.0 g, 2.33 mmol) was dissolved in dry diethyl ether (100 mL) under gentle stirring and the resulting mixture was dried at -78 ° C using a dry ice, acetone bath. By cooling. To this mixture, 1.52 M n-butyllithium / n-hexane solution (3.2 mL, 4.94 mmol) was added dropwise for 10-15 minutes. The solution was warmed to room temperature and stirred for 3 hours to complete the lithiation reaction. The resulting mixture was cooled back to -78 ° C and TiCl ₄ (0.25 mL, 2.32 mmol) was added dropwise. The solution was warmed to room temperature and stirred for 15-18 hours to give a dark red brown solution. The solution was condensed in vacuo to yield crude (A) as a dark brown solid. A 50.0 mL portion of dichloromethane was added to the crude (A) and stirred for 5 minutes and then filtered through a sinter funnel of medium porosity G-2. This step was repeated twice (50 mL dichloromethane-each time) to remove all solid impurities from the crude (A). The organic filtrate (DCM extract) was combined and dried in vacuo to yield a brown solid. This solid was washed with n-hexane / diethyl ether (95: 5) solution (3 times, 20 mL solution each time), followed by n-hexane (20 mL) to give pure (mono chelate) (A) reddish brown Solid (1.3 g, yield 97%).

Similarly, the synthesis yields bis chelates when the ligand: TiCl ₄ mole ratio is 2: 1 and tris chelates when the ligand: TiCl ₄ mole ratio is 3: 1.

Characterization data

a. (A) Formula I wherein the substituent is:

R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ _, R ¹⁰ , R ¹¹ , R ¹² are hydrogen; R ⁵ and R ⁹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer of 2.

Procatalyst: C ₂₈ H ₃₀ Cl ₂ N ₂ O ₂ Ti d; Molecular formula

Elemental Analysis: C: 61.35% (Theoretical: 61.67%), H: 5.31% (Theoretical: 5.54%), Cl: 13.52% (Theoretical :: 13: 00%), N: 5.09% (Theoretical: 5.14%), Ti 8.54% (theoretical: 8.78%).

Catalysts of this type are known to form positive complexes in Lewis acids. This makes it difficult to obtain accurate mass spectra for these sensitive catalysts when using the EI and CI methods. Even trace moisture can generate HCl in Ti chelates to form adducts as positive equivalents of the catalyst component. Nevertheless, indirect traces of the presence of Ti and Cl from elemental analysis except for dark red brown are sufficient to reach the proposed molecular / experimental formula.

The mass spectrum (FIG. 3) taken by the EI (electron ionization) method shows a peak at 617.53 m / z, which corresponds to the adduct of molecular ions (mass 545.46) in pentane (mass 72). Pentane gas is used in the EI method for mass spectral analysis. In the CI (chemical ionization) assay mode (FIG. 4), only a ligand peak of 428.56 m / z appears as the catalyst decomposes into a stable ligand moiety in the CI mode.

B. Formula (I) wherein the substituent is as follows:

R ¹ and R ² , R ³ , R ⁴ , R ⁶ , R ⁸ _, R ¹⁰ , R ¹² are hydrogen; R ⁵ and R ⁹ , R ⁷ and R ¹¹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer of 2.

Procatalyst: Molecular Formula of C ₃₆ H ₄₆ Cl ₂ N ₂ O ₂ Ti

Elemental Analysis: C: 65.54% (Theoretical: 65.76%), H: 7.11% (Theoretical: 7.05%), Cl: 11.12% (Theoretical: 10.78%), N: 4.15% (Theoretical: 4.26%), Ti: 7.15 % (In theory: 7.28%).

The mass spectrum (FIG. 5) taken by EI (electron ionization) shows a peak at 541.48 m / z, corresponding to the ligand portion of the claimed catalyst (mass 540.1). During the EI mode analysis, the catalyst decomposes into stable ligand moieties. Other relevant analytical data on Ti and Cl content demonstrate the proposed formula for the catalyst. The procatalyst also effectively polymerizes ethylene and would not be the case unless it was a ligand.

c. Cost, toxicity, rate profile, reactor Fouling , Catalysts of the prior art Procatalyst (A)  Containing By comparing catalyst Procatalyst (A)  Shows that the containing catalyst is more efficient than the prior art catalyst

Prior art catalysts that effectively produce unwrapped ultrahigh molecular weight polyethylene contain pentafluoro aniline components in the ligand moiety. Unlike prior art catalysts, transition metal catalysts containing a procatalyst (A) do not have a pentafluoro aniline component, which makes the procatalyst more environmentally friendly compared to existing prior art catalysts.

Transition metal catalysts containing the procatalyst (A) are very economical as they do not have an expensive pentafluoro aniline component compared to prior art catalysts.

Prior art catalysts show a rapid reaction rate profile (shown in the graph of FIG. 1) where the polymerization temperature increases by itself to 55 ^o C at room temperature for 4-5 minutes to remove the cryostat. Improper use may result in fouling of the polymerization reactor. On the other hand, under the same polymerization conditions, the transition metal catalyst including the procatalyst (A) shows a slower reaction rate (as shown in the graph below), where the polymerization temperature is slowly increased from room temperature to maximum temperature 35-40. Increases in minutes. Since the catalyst with procatalyst (A) shows controlled reaction rates, fouling of the reactor at temperatures of approximately 60 ° C. due to slow, stable and uniform polymer formation which prevents lump formation even in the absence of cryostats. Can be prevented.

In addition to having a rapid kinetic profile, the prior art catalysts also show the inherent ethylene polymerization properties of rapidly increasing molecular weight of the polymer. This in turn shows that at low molecular weights of 1-6 million g / mole, it is particularly difficult to control the molecular weight of the polymer with the desired yield of the polymer. Transition metal catalysts, including procatalysts (A), show controlled slow reaction rates, which is advantageous for improving process control, in particular for achieving molecular weights of 1-6 million g / mole and with increasing polymer yields. Do. MW of 1-6 million g / mole is ideal for facilitating polymer treatment, so transition metal catalysts including the procatalyst (A) are efficient with regard to processes that achieve productivity and desired molecular weight.

The graph shown in FIG. 2 shows the effect of the co-catalyst / catalyst (Al / Ti) ratio in the polymerization profile for both catalysts. Co-catalyst not only activates the catalyst but also acts as a chain finishing agent to control the molar mass, so increasing the Al / Ti ratio of the transition metal catalyst including the precatalyst (A) leads to a decrease in molecular weight. In the case of prior art catalysts, the MW increases by Al / Ti ratio and also in its original nature. The transition metal catalyst comprising procatalyst (A) thus shows better control of MW in the 1-6 million g / mole region.

The transition metal catalyst including the procatalyst (A) can achieve the desired molar mass with improved productivity as compared to prior art catalysts. See Table 1 below.

Action of Transition Metal Catalysts Including Procatalyst (A) in the Preparation of Unwrapped Ultrahigh Molecular Weight Polyethylene Compared to Prior Art Catalysts catalyst * Al / Ti Yield (g) Yield (g / g cat) Time (m) MW of Million (g / mol) at ASTM Scale Catalyst with Procatalyst A 222 340 850 180 2 Catalyst with Procatalyst A 222 440 1100 180 1.9 Catalyst with Procatalyst A 208 460 1050 180 2.72 Prior art catalyst 220 430 843 45 6.8 Prior art catalyst 220 330 647 45 6.9 Prior art catalyst 257 440 863 45 7.1

Al is from PMAO with cocatalyst. The polymerization proceeds under 500 rpm agitation at 2.5 bar ethylene pressure in Barsol as the medium. The reactor is made of SS316 metal and has a capacity of 19L.

The functional properties (by lithiation and non-lithiation routes) of transition metal catalysts including the procatalyst (A) in the preparation of unwrapped ultrahigh molecular weight polyethylene under different process conditions are provided in Table 2 below to illustrate the results. A typical polymerization reaction proceeds with the addition of PMAO as a co-catalyst using a 500 mL polymerization medium in a 1 L Buchi Polyclave glass reactor followed by addition of the catalyst and ethylene at ambient temperature (26-28 ° C.). Stirring speed is 500 rpm.

catalyst Catalyst (mg) C2 pressure (bar) Al / Ti Minutes Yield (g / g catalyst) MW of Million (g / mol) at ASTM Scale Polymerization medium Catalyst containing procatalyst A prepared with lithiated route 18 2.5 84 60 543 4.5 Barsol 18 2.5 141 60 1315 3.5 18 2.5 141 180 1327 5.9 18 2.5 248 45 1554 1.3 18 2.5 248 60 1768 1.8 18 2.5 248 120 2071 2.9 Catalyst containing procatalyst A prepared with lithiated route 16.5 2.5 215 120 4200 3.9 Barsol 16.0 2.5 215 120 4400 3.8 17.3 2.5 215 120 4300 4.0 18.0 2.5 215 120 4400 3.9 8.0 2.5 215 120 3900 5.7 7.5 2.5 215 120 4100 5.5 Catalyst containing procatalyst A prepared with lithiated route 18 2.5 215 180 5000 4.2 Barsol 18 5.0 215 180 5700 4.2 14 5.0 215 180 6700 5.3 12 5.0 215 180 5400 5.5 10 7.0 215 180 5400 5.8 18 0.5-1.0 215 360 5300 7.1 (polymerization at 15 ° C.) 18 0.5-1.0 215 180 5200 6.2 (polymerization at 15 ° C.) Catalyst containing procatalyst A prepared with lithiated route 18 2.5 215 180 4200 4.8 toluene Catalyst containing procatalyst A prepared with lithiated route 18 2.5 215 180 4400 4.7 (Polymerization Media Hexane) Hexane Catalyst containing procatalyst A made from non-lithiated route 16.5 2.5 215 180 4300 4.1 Barsol 16.0 2.5 215 180 4100 4.0 17.5 2.5 215 180 4400 4.5 18.5 2.5 215 180 4600 4.6 Catalyst containing procatalyst B prepared with lithiated route 20.4 2.5 215 180 3800 3.9 Barsol 16.0 2.5 215 180 3700 4.0 Catalyst containing procatalyst B made from non-lithiated route 20.7 2.5 215 180 3850 3.5 Barsol 18 2.5 215 180 3500 3.7

Most of the polymerization reactions showed a fairly controlled rate profile and proceeded at temperatures of 45-48 ° C.

The polyethylene obtained in all the above experiments had a fiber and porous morphology, a bulk density of 0.05-0.1 g / cc, high crystallinity (obtained from DSC and XRD).

A SEM image of one representative polymer sample showing fiber and porous morphology is illustrated in FIG. 6.

XRD of one representative polymer sample showing high crystallinity is illustrated in FIG. 7.

DUHMPE obtained using a transition metal catalyst with a procatalyst (A) is capable of stretching below the melting point in all respects (low bulk density of 0.05-0.10 g / cc; improved crystallinity 95-99%) in terms of XRD And in fiber / pore form are the same as the DHHMWPE obtained by the prior art catalyst.

[Effects of the Invention]

The novel transition metal based procatalyst of the present invention effectively controls the polymerization reaction rate and more efficiently adjusts the molecular weight, thus making the polymerization process economical and environmentally friendly.

The transition metal based procatalyst of the present invention, unlike the polymerization process using prior art catalysts, prevents fouling of the polymerization unit.

Throughout this description the term "comprise", or variations such as "comprises" or "comprising" means the inclusion of the element or integer, step, or group of elements or integers, steps mentioned, It should be understood that it does not mean the exclusion of any other element or integer, step, or group of elements or integers, steps.

The use of the expression "at least" or "at least one" implies the use of one or more elements or components or amounts, which use is carried out in the practice of the invention to one or more preferred purposes. To achieve the results or results.

The discussion of documents, materials, devices, products, and the like contained in this manual is merely for the purpose of providing a context for the present invention. It is not admitted that any or all of these existed anywhere prior to the priority date of the application, and thus they are part of the prior art base and become common knowledge in the field related to the present invention.

Numerical values stated for various physical parameters, or sizes, or quantities are approximate and are not intended to be greater than / less than the numerical values assigned to the parameter, size, or quantity, unless otherwise indicated in this specification. You should expect to be in range.

While considerable emphasis has been placed on the features of the preferred embodiments, it will be appreciated that many additional features may be added and many changes may be made to the preferred embodiments without departing from the principles of the invention. These or other variations of the preferred embodiment of the present invention will be apparent to those skilled in the art from this description, it should be clearly understood that the foregoing descriptions are merely illustrative of the present invention and not limiting.

The foregoing descriptions of specific embodiments fully illustrate the general nature of the invention so that others may readily apply existing knowledge to modify and / or adapt these specific embodiments in various applications without departing from the general concept, Accordingly, such changes and adaptations are to be understood and intended within the spirit and scope of equivalents of embodiments of the present invention. The expressions and predicates used herein are for the purpose of description and not of limitation. Therefore, although embodiments of the invention have been described with reference to suitable embodiments, those skilled in the art will recognize that embodiments of the invention may be practiced.

Claims (19)

In the transition metal based procatalyst represented by the formula (I),

Formula I
R ¹ , R ² , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ and R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R ⁵ and R ⁹ are tertiary alkyl groups;
R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and tertiary alkyl groups;
R ³ is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl group and sulfone group;
M is a group consisting of hafnium (Hf), manganese (Mn), iron (Fe), rhenium (Re), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V) and titanium (Ti) Transition metal selected from;
X is a halide selected from the group consisting of Cl, Br and I;
n is an integer of 2, a transition metal based procatalyst.
The method of claim 1, wherein the procatalyst is
i. R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ and R ¹² are hydrogen; R ⁵ and R ⁹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer of 2; And
ii. R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ and R ¹² are hydrogen; R ⁵ , R ⁹ , R ⁷ and R ¹¹ are tertiary butyl groups; M is titanium (Ti); X is Cl and n is an integer of 2
A transition metal based procatalyst, consisting of a set of substituents selected from the group consisting of:
In the method for producing a transition metal-based procatalyst according to claim 1,
i. Reacting the aromatic diamine of formula (II) with at least one substituted salicylicaldehyde of formula (IIIa / IIIb) to obtain a sieve base imine ligand of formula (IV):

Formula (II) Formula (IIIa) Formula (IIIb) Formula (IV)
Wherein R ¹ , R ² , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ and R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R ⁵ and R ⁹ are tertiary alkyl groups;
R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;
R ³ is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl group and sulfone group);
Ii. Optionally, at a temperature in the range of −78 ° C. to room temperature, the alkali metal salt of the Schiff base imine ligand of Formula (V) is added by adding an alkali metal ion to the Schiff base imine ligand of Formula (IV) using an alkali metal ion additive. Obtaining:

Formula (IV) Formula (V)
Wherein R ¹ , R ² , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ and R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R ⁵ and R ⁹ are tertiary alkyl groups;
R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;
R ³ is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl group and sulfone group;
M ₁ is an alkali metal ion of an alkali metal ion additive); And
Iii. At a temperature in the range of −78 ° C. to room temperature, a transition metal represented by Formula I by chelating an alkali metal salt of the Schiff base imine ligand of Formula IV or the Schiff base imine ligand of Formula (V) with a transition metal halide Obtaining the Based Procatalyst:

Formula I
Wherein R ¹ , R ² , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ and R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R ⁵ and R ⁹ are tertiary alkyl groups;
R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;
R ³ is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl group and sulfone group;
M is a group consisting of hafnium (Hf), manganese (Mn), iron (Fe), rhenium (Re), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V) and titanium (Ti) Transition metal selected from;
X is a halide selected from the group consisting of Cl, Br and I;
n is an integer 2);
Method for producing a transition metal-based procatalyst comprising a.
The method of claim 3, wherein the ratio of the alkali metal salt of the sieve base imine ligand of formula IV or the sieve base imine ligand of formula (V) to the transition metal halide is 1: 1.
The process of claim 3, wherein step i is selected from at least one liquid medium selected from the group consisting of toluene, xylene, hexane, methanol and ethanol, at a temperature ranging from 40 ^° C. to a boiling point of the liquid medium. Wherein the process is carried out in the presence of at least one compound selected from the group consisting of sulfonic acid and sulfuric acid.
The method according to claim 3, wherein the substituted salicyaldehyde is at least one compound selected from the group consisting of 3-tert-butyl salicylaldehyde and 3,5-di-tert-butyl salicylaldehyde.
The method of claim 3, wherein the substituted salicylaldehyde of formula (IIIa) and the substituted salicylaldehyde of formula (IIIb) are the same or different.
The method of claim 3, wherein the procatalyst is
i. R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ and R ¹² are hydrogen; R ⁵ and R ⁹ are tertiary butyl groups; M is titanium (Ti); X is Cl; n is an integer of 2; And
ii. R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ and R ¹² are hydrogen; R ⁵ , R ⁹ , R ⁷ and R ¹¹ are tertiary butyl groups; M is titanium (Ti); X is Cl; n is an integer of 2
It consists of a set of substituents selected from the group consisting of.
The method of claim 3, wherein the alkali metal ion additive is at least one selected from the group consisting of n-butyl lithium, sodium hydride, lithium aminoalkoxide and lithium diisopropylamide.
In the catalyst composition,
i. A transition metal based procatalyst represented by formula (I),

Formula I
Where
R ¹ , R ² , R ⁴ , R ⁶ , R ⁸ , R ¹⁰ and R ¹² are the same or different and are independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R ⁵ and R ⁹ are tertiary alkyl groups;
R ⁷ and R ¹¹ are the same or different and are independently selected from the group consisting of hydrogen and a tertiary alkyl group;
R ³ is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl group and sulfone group;
M is a group consisting of hafnium (Hf), manganese (Mn), iron (Fe), rhenium (Re), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V) and titanium (Ti) Transition metal selected from;
X is a halide selected from the group consisting of Cl, Br and I;
n is an integer of 2; a transition metal based procatalyst;
Ii. At least one alkyl aluminum co-catalyst; And
Iii. A catalyst composition comprising at least one inert hydrocarbon liquid medium.
The method of claim 10, wherein the alkyl aluminum co-catalyst is methylaluminoxane, poly-methylaluminosane, triethyl aluminum, isoprenyl aluminum, aluminum sesquichloride, tri-n-octyl At least one compound selected from the group consisting of aluminum and triisobutyl aluminum.
The catalyst composition of claim 10, wherein the co-catalyst is poly-methylaluminosane.
The catalyst composition of claim 10, wherein the ratio of elemental aluminum to elemental titanium (Al / Ti) is in the range of 50: 1 to 1000: 1.
The method of claim 10, wherein the inert hydrocarbon liquid medium is at least one selected from the group consisting of pentane, hexane, cyclohexane, methyl cyclohexane, heptane, octane, decane, toluene, isopentane and mineral spirit. , Catalyst composition.
The catalyst composition of claim 10, wherein the ratio of elemental aluminum to elemental titanium (Al / Ti) is between 200: 1 and 300: 1 and the inert hydrocarbon liquid medium is mineral spirit.
In the polymerization of olefins, the process is:
i. The transition metal based procatalyst of claim 1 and the at least one co-catalyst, in the presence of at least one inert hydrocarbon liquid medium, in a ratio of 50: 1 to 1000: 1 of elemental aluminum to elemental titanium. At a temperature ranging from 10 ° C. to 30 ° C., to obtain the activated catalyst composition,
ii. Adding at least one olefin monomer to the activated catalyst composition to obtain a reaction mixture, and
iii. Polymerizing the reaction mixture at a temperature of 5 ° C. to 70 ° C. and a pressure of 0.1 to 11 bar for a time period ranging from 1 hour to 10 hours to obtain a polymerized olefin.
The polymerization of olefins according to claim 16, wherein the inert hydrocarbon liquid medium is at least one selected from the group consisting of pentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, decane, toluene, isopentane and mineral spirits. fair.
The process of claim 16, wherein the olefin monomer is ethylene and the inert hydrocarbon liquid medium is mineral spirit. delete

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